CN1087310C - Fluorinated acrylic and methacrylic latices and mixtures thereof, processes for manufacturing them and their application in field of hydrophobic coatings - Google Patents
Fluorinated acrylic and methacrylic latices and mixtures thereof, processes for manufacturing them and their application in field of hydrophobic coatings Download PDFInfo
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- CN1087310C CN1087310C CN95118631A CN95118631A CN1087310C CN 1087310 C CN1087310 C CN 1087310C CN 95118631 A CN95118631 A CN 95118631A CN 95118631 A CN95118631 A CN 95118631A CN 1087310 C CN1087310 C CN 1087310C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/22—Esters containing halogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
Abstract
This fluorinated (meth)acrylic latex consists of a dispersion of particles or of a mixture of dispersions of particles, these dispersions being obtained by emulsion polymerization in an aqueous medium, in at least one stage, wherein one more perfluorinated monomer(s) of formula (I) has/have been used as sole fluorinated comonomer(s) for the formation of the particles, and which is/are distributed statistically in particles formed in one stage or distributed statistically in the shell of structured particles of the core-shell or core-intermediate layer(s)-shell type resulting from a polymerization in two stages and in more than two stages, the proportion of monomers of formula (I): R1=CH3 or H; R2=perfluorinated C1-C10 alkyl; and 0<n</=4.
Description
The present invention relates to the fluorate acrylic acid of low fluorine content and methacrylic latices and composition thereof, and the method for preparing them.
" latex " is meant the aqueous dispersion of polymer particles that is for example obtained by emulsion polymerization.
These dispersions participate in forming as the composition that is coated with for example to be intended; by spraying, flat smear, the method for roller coat, brushing, spraying, threaded rod or dipping; on matrix; for example on concrete, brick, cement brick, timber, synthetic textiles, leather, metal, old coating etc., form uniform deposition thing according to desired thickness; make attached layer at ambient temperature after the drying, have hydrophobic supercoat.As the example of these coating compositions, can mention be used for building field japanning various in style (for example exterior paint, plucking plaster or the like), leather with varnish, leather and fabric with finishing agent, timber with varnish or the like.The present invention also relates to all these application.
As the monomer that can make this class latex have hydrophobic property, can be formula (I) monomer:
In the formula :-R
2Represent CH
3Or H;-R
2Represent perfluor C
1-C
10The alkyl atomic group; With-0＜n≤4, and distinguishingly can be (methyl) vinylformic acid 2,2, the 2-trifluoro ethyl ester
The polymerization of trifluoroethyl methacrylate is various research topics always, to obtain being used as physiologically active substance carrier (JP-A-61-019,615 stable in saline media; EP-A-182,516; JP-A-61-274,260; JP-A-62-100,511), as static inhibitor (JP-A-63-092,623 of electrofax developer; JP-A-63-092,606) and as coating (FR-A-2,656,316; JP-A-05,140,237; JP-A-04,248,821; EP-A-408,422) polymeric dispersions.
For obtaining having three or four layers and in these fluorinated monomers, have the higher weight composition particle of (being about 75-95%) of different nature, also narrated based on (methyl) vinylformic acid 2,2, preparation (JP-A-59-147,011, the 59-147 of the structure particles dispersion of 2-trifluoro ethyl ester, 010,59-122,512,59-124,915,59-098,116 and 59-07,411).The purpose of using these polymkeric substance is to coat photoconductive fiber, and the film that is got by these polymer beads of fusing has excellent water tolerance and oil-proofness.In these patent documentations, therefore the gained polymerization can not use them to make hydrophobic coating, for example japanning and finishing agent because their second-order transition temperature is very high.
Stable and can be in order to obtain in saline media as the dispersion of physiologically active substance carrier, polymerization methacrylic acid 2,2, the 2-trifluoro ethyl ester with structure particles also developed (JP-A-63-228,069,01,040,510,01,144,403 and 01,170,854).Methacrylic acid 2,2, the 2-trifluoro ethyl ester limits the polymerization of (methyl) vinylformic acid in water exactly as the effect of hydrophobic monomer, and promotes it to infiltrate in this particulate shell.In the case, because the second-order transition temperature of polymkeric substance is too high, they can not be used as coating.
Contain with as the methacrylic tert-butyl acrylate of shell and as a kind of bonded methacrylic acid 2 in the neutral acrylic acid or the like of the methyl methacrylate/butyl acrylate of nuclear/, 2,2-trifluoro ethyl ester or methacrylic acid 2,2,3, the synthetic of the structure particles of 3-tetrafluoro propyl ester described in (JP-05,148,122) as participating in the nail oil composition.
Fluoridize powder in order to obtain organic soluble,, narrated in 480 and fluoridized the synthetic of structure particles also at EP-393.In the case, this particulate nuclear is made of tetrafluoroethylene and shell is made of fluorinated acrylate.
Thereby will be noted that, at the methacrylic acid 2,2 of touching upon, in the patent documentation of 2-trifluoro ethyl ester letex polymerization, almost do not do relevant invention by the coalescent invention that the hydrophobic coating dispersion is provided of particulate.
And known latex mixture constitutes the technology of improving the latex performance.Thereby, the latex that might life should have useful performance, and sneak in the latex with desired properties as masterbatch with this latex.The degree of the useful performance of gained generally is between two kinds of latex performances, and depends on each the relative proportion in two kinds.
In adhesive field, known adhesive power (" viscosity " performance) is mainly composed preface by the polymkeric substance with respect to inferior quality (mass), and the polymkeric substance of better quality has improved the adhesive property of bonding film.Therefore use with latex mixture of these characteristics has constituted the useful means that obtain required quality polymolecularity, and this is more easier than the method by direct polymerization.
Latex mixture also can be used to play makes the crosslinked purpose of film at particle aggregation with when interpenetrating.When this situation, synthetic respectively two kinds of latex with chemical incompatible functional group.Then these latex are mixed, between these particles, do not cause chemical reaction, and allow suitable period of storage.On the contrary, during these particles interpenetrate, chemical reaction takes place and make that the bonding use and the mechanical property of film are strengthened.At for example European patent EP-195,661 and EP-176, disclose by mixing these two kinds of composition systems that latex obtains in 609.
With methacrylic acid 2,2, the 2-trifluoro ethyl ester is that the small amount of fluorine atom of matrix needs a large amount of this monomers that add when polymer formation, so that obtain gratifying hydrophobic property.Therefore, in described application (fibre-optic coating or the like) have hydrophobic property, it is sizable needing the quantity of this relatively costly fluorinated monomer as can be seen; For application of the present invention, these quantity are than big from quantity that economic consideration allowed, and this relates to wants to make the product problem of (japanning, varnish or the like) that extensively distributes.
Owing to these reasons, thereby invention is intended fluoridizing latex (fluorinated monomer of described type can be participated in to optimize quantity wherein) with the synthetic dispersion that obtains hydrophobic coating by cohesion, can be to our the sizable improvement of knowledge composition in this field, and can promote that these fluorinated monomers use in the related Application Areas.
So, the applicant attempts near under the room temperature condition and do not needing under excessive coalescing agent (for example phenylcarbinol, the fourth glycol ether or the like) condition, by coalescence effect, improvement can provide that hydrophobic performance applies by fluoridizing filming that (methyl) acryllic acid latex forms.These new type latexes have reduced the content of fluorinated monomer widely, even so, still keep useful hydrophobic property, have promptly reduced because the wetting capacity and increased wet abrasion intensity of filming that water causes.
Be astoundingly, use comprises the latex of fluoridizing with structure particles of being rich in the fluorinated monomer shell, and using the mixture of fluoridizing latex and nonfluorinated latex just can reach this purpose, these fluoridize the advantageously above-mentioned latex of fluoridizing that comprises structure particles of latex.Of the present invention when fluoridizing latex and nonfluorinated latex blended situation, even what more make us being surprised is that resulting characteristic surpasses or equals initial characteristic of fluoridizing latex, and is not in moderate between the characteristic of the latter's characteristic and nonfluorinated latex.According to the analysis of being carried out, adapting from layering of the good hydrophobic performance that maintenance is filmed and this polymer coating film has capillary the fluoridize latex lower than nonfluorinated latex and moves in air/polymkeric substance interface, so that reduce the energy of system.
Theme of the present invention is exactly a kind ofly to fluoridize (methyl) acrylic latex by a kind of particle dispersion or by what a kind of mixture of particle dispersion constituted, these dispersions are with single order section at least, letex polymerization obtains in water medium, wherein perfluorinated monomers in institute's definition (I) has been used as and has formed the unique comonomer of fluoridizing of particulate above one or more, and its (they) statistical distribution in the formed particle in a stage respectively, perhaps statistical distribution in the shell of the structure particles of two-stage or the nuclear-shell that in more than the two-stage polyreaction, generates or nuclear-middle layer-shell type.Described latex is made of a kind of described structure particles dispersion, perhaps describedly fluoridizes structure particles and/or at least a described mixture of fluoridizing statistics particulate dispersion and at least a nonfluorinated statistics particulate dispersion constitutes by at least a.Monomer in the formula (I) or the representative of a plurality of monomer are less than the shell of fluoridizing structure particles of 80% (weight), to be used to form all described latex (forming at least) particulate total monomer amount from a kind of dispersion is benchmark, monomeric ratio is between 1.8 to 20% (weight), distinguishingly between 2 to 10% (weight) in the formula (I).
Can come these numerical value of comparison with 35 to 70% scope, wherein 35 to 70% scope is exactly can produce fluoridizing of same at least hydrophobic performance to add up particulate numerical value, is with (comparison between face table 1 and the table 2 as follows) of measuring contact angle or measuring with the method for measuring wet abrasion intensity.
Preferably, monomer (I) is (methyl) vinylformic acid 2,2, the 2-trifluoro ethyl ester.
Participation is fluoridized or the monomeric character and the ratio of the composition of the different steps of nonfluorinated statistics particle and structure particles; choose in such a way: constitute the described statistics particle or the glass transition temperature of polymer in described structure particles stage and be less than or equal to 40 ℃; especially between-5 to 25 ℃; therefore the good formation characteristic of filming be can keep, and demanding application of temperature and excessive a large amount of coalescing agent do not needed.
The particularly preferred embodiment according to the present invention is fluoridized statistics particulate monomer and is formed, and perhaps fluoridizes the monomer [by weight, total amount is 100% (weight)] composed as follows of structure particles shell :-20-80%, at least a monomer (I) of 35-70% especially;-20-80%, preferably at least a of 20-55% can produce (methyl) vinylformic acid or the vinyl monomer with lower glass transition temperatures homopolymer;-0-30%, preferably at least a of 0-15% can produce (methyl) vinylformic acid, vinylbenzene or the vinyl monomer with high glass-transition temperature homopolymer;-0-10%, preferably at least a carboxylic acid (methyl) Acrylic Acid Monomer of 0-2%;-0-3%, preferably at least a crosslinked (methyl) propionic acid monomer of 0-2% reaches-0-5%, preferably at least a hydrophilic (methyl) Acrylic Acid Monomer of 0-2%.
In foregoing, " lower glass transition temperatures " is meant general temperature between-80 to-20 ℃; " high glass-transition temperature " is meant general temperature between+10 to 200 ℃.
Can for example select in ethyl propenoate, butyl acrylate, 2-EHA and the vinylformic acid ester in the ninth of the ten Heavenly Stems to produce a kind of (methyl) Acrylic Acid Monomer expediently from (methyl) alkyl acrylate with lower glass transition temperatures homopolymer.Especially, this class vinyl monomer is the 2 ethyl hexanoic acid vinyl acetate.
Especially, can produce a kind of (methyl) Acrylic Acid Monomer with high glass-transition temperature homopolymer is methyl methacrylate.Especially, this class vinyl monomer is a vinyl acetate.Especially, this quasi-styrene monomer is a vinylbenzene.
In the middle of carboxylic acid (methyl) Acrylic Acid Monomer, mention vinylformic acid and methacrylic ether especially.
Especially, from hydrophilic crosslinked dose, for example N-methylol (methyl) acrylamide and (isobutoxy methyl) acrylamide, and from hydrophobic crosslinking agent, for example two (methyl) vinylformic acid ethylene-alcohol ester, two (methyl) vinylformic acid butanediol ester, two (methyl) vinylformic acid hexylene glycol ester and first are selected cross-linking monomer in acrylic anhydride.
With regard to hydrophilic (methyl) acrylic acid copolymer monomer, select ethyl-imidazolone (methyl) acrylate and acrylamide especially.
With regard to nonfluorinated statistics particulate monomer is formed with the monomer of fluoridizing structure particles nuclear, its composition following especially [by weight, total amount is 100% (weight)]:---20-80%, at least a can the production of 40-70% has reduced TG transformation temperature especially
(methyl) vinylformic acid or the vinyl monomer of degree homopolymer;---20-80%, at least a can the production of 30-60% has the high glass transition temperature especially
(methyl) vinylformic acid, vinylbenzene or the vinyl monomer of degree homopolymer;---0.5-10%, at least a carboxylic acid (methyl) Acrylic Acid Monomer of 0.5-2.5% especially;---0.3-5%, 0.5-3%'s is at least a crosslinked especially, (methyl) Acrylic Acid Monomer; And
Under structure particles nuclear situation,---0-0.3%, but especially 0-0.2% at least a cross-linking monomer be difunctionality under the N hydroxymethyl acrylamide situation compatible or grafted monomer.
As producing monomer with low Tg homopolymer, can produce monomer with high Tg homopolymer, participate in carboxylic (methyl) Acrylic Acid Monomer and the cross-linking monomer of above-mentioned composition, can fluoridize the statistics particle and form with top pointed formation and fluoridize the identical of structure particles shell.But with regard to compatible or grafted monomer, select these monomers especially from diallyl maleate, (methyl) allyl acrylate and tetramethylene dimethacrylate, the latter also is a linking agent.
Also can use to be different from (methyl) vinylformic acid 2,2, fluorinated monomer in the formula of 2-trifluoro ethyl ester (I), for example a kind of (methyl) vinylformic acid (perfluorinated alkyl) ethyl ester is as the shell comonomer of statistics or structure particles.Yet these monomeric uses have improved the price of polymkeric substance, and this is not desirable in practice.
Fluoridize particle for structure, the part by weight of shell is preferably 3 to 30%, is preferably the described particle of 5 to 20% (weight), and this particle size is between 100 to 300nm, in addition, this particle size generally is that the hydrophobic coating film that generates in order to make has enough luster performances.
According to the present invention, latex particle concentration by total dispersion weight, is generally 10 to 65%, especially between 40 to 55%.
Theme of the present invention also is a kind of method for preparing above-mentioned latex, it is characterized in that preparing the water dispersion of fluoridizing (methyl) acrylic particles of at least a nuclear-shell or nuclear-middle layer-shell structure, and monomer or monomer (I) participate in the formation of described particle shell; It is characterized in that,, dispersions obtained and another kind of dispersion is mixed in suitable occasion; And it is characterized in that, in suitable occasion, obtaining dispersion or multiple dispersion are mixed with the water dispersion that at least a nonfluorinated is added up (methyl) acrylic particles; Perhaps it is characterized in that alternatively preparing at least a statistics (methyl) the acrylic particles water dispersion of fluoridizing with one or more compounds of the comonomer in the formula (I); It is characterized in that,, mix with another dispersion dispersions obtained in suitable occasion; And it is characterized in that, the dispersion or the multiple dispersion that are generated are mixed with the water dispersion that at least a nonfluorinated is added up (methyl) acrylic particles, all above-mentioned water dispersions be by according to circumstances with a stage or multistage more, emulsion polymerisation process is made in water medium.
The particle dispersion that can have nuclear-shell or shell-middle layer-shell structure with following currently known methods preparation:
Do not causing in the presence of the new granuloplastic emulsification system that (a) monomer (I) monomer mixture is rich in polymerization on a seed that does not contain any monomer (I);
(b) by mixing two kinds of mixtures (according to " shooting " type method) in proper order or can at leisure second kind of mixture being incorporated in first kind of preemulsion, so that set up a kind of method of bringing compatible components gradient between nuclear and the shell, two kinds of monomer mixtures of polymerization progressively, first kind of monomer do not contain any monomer (I) and second kind of monomer contains some monomers (I).
According to the technology described in the document, can be by adopting grafted monomer or the method for mhc monomer being grafted on shell on the nuclear, preferably, for example when reaching after the 75-80%, consideration conveyization introduces in nuclear polymerization latter stage.
Preferably by using, the method that for example resembles top pointed cross-linking monomer increases the quality of granular core.Yet for fear of any problem takes place during particles coalesce, the crosslinked of nuclear should too do not spent.By using (methyl) vinylformic acid N-hydroxyl methyl alcohol ester, can obtain satisfied effect.The increase of fluoridizing the structure particles nuclear mass can be avoided any reorganization of this particle form, and fluorinated polymer is retained in the shell.In fact, the result is that the hydrophobicity of monomer or monomer (I) is stronger, contains this/these polymer of monomers and certainly will move to this particulate inside.
Similarly, for the coating of the nuclear that promotes to have the shell fluorinated polymer, preferably for shell, do not have too high quality, and when the shell polyreaction, add an amount of chain-transfer agent, for example alkyl sulfhydryl (lauryl mercaptan, uncle's lauryl mercaptan) or Thiovanic acid.Yet the consumption of chain-transfer agent should be too not high, in order to avoid weaken the final mechanical property of this polymer coating film.With respect to the monomer that is incorporated in the shell, can use to be up to 0.5% (weight), preferably be up to the chain-transfer agent of 0.3% (weight).
Also a certain amount of linking agent can be introduced and have in the shell of an amount of chain-transfer agent.
Although monomer (I) is introduced generation difficulty in the core-shell type particulate nuclear,, be preferably in this particulate nuclear and do not mix this monomer (I), so that do not increase the cost of latex according to the present invention.In addition, not mixing of this monomer (I) can cause the improvement that hydrophobic property is big in nuclear.
Be used for composite structure particulate initiator system and can be for example K
2S
2O
8, (NH
4)
2S
2O
8/ Na
2S
2O
5, Na
2SO
3Redox system, (NH for example
4)
2S
2O
8Hot system or for example 2,2 '-the water dissolvable azo-compound of the dihydrochloride (V.50 (WACO)) of azo two (2-amidine propane).Preferred system is (NH
4)
2S
2O
8/ Na
2S
2O
5With independent use (NH
4)
2S
2O
8Redox system.With the monomer is benchmark, and its consumption is in 0.2 to 0.5% (weight), preferably between 0.25 to 0.35% (weight).
From the emulsifying agent with suitable hydrophobic/lipophilic balance is to select to be used to prepare the particulate emulsification system the agent.Best system is made up of with combining of nonionogenic tenside (NONYL PHENOL ETHOXYLATED and the fatty alcohol ethoxylate that for example contain 10-40mol oxyethane) anion surfactant (the nonyl phenol sulfuric ester, dodecylbenzene sulfonate and the fatty alcohol ethoxylate sulfuric ester that for example comprise 20-25mol oxyethane).Preferred system is to be 50: 50 to 85: 25 the NONYL PHENOL ETHOXYLATED sulfuric ester that contains 25mol oxyethane and to contain the combination of the NONYL PHENOL ETHOXYLATED of 25mol oxyethane with preferred weight ratio.With respect to monomer, total consumption of emulsifying agent is 2 to 4% (weight), is preferably 2.5 to 3.5% (weight).
By semicontinuous type method, can preferably carry out preparation according to structure particles dispersion of the present invention, can decide on the active ratio of different monomers, be limited in the composition deviation in nuclear-shell scope, yet the polyreaction of in batches examining is possible.
Generally use according to latex of the present invention, perhaps use with the form of latex mixture with their forms own.Can be the mixture of at least two kinds of latex especially, a kind of latex contains the monomer (I) of q.s to reduce the surface tension of polymkeric substance rightly, and another kind of latex does not contain any monomer (I).Although it does not constitute the conclusive characteristics of the present invention, can form a kind of mixture with one or more nonfluorinated latex by several latex (containing statistics or structure particles) of fluoridizing with identical or different content monomer (I).Similarly, also it is contemplated that a kind of latex based on monomer (I) is mixed with a kind of latex based on a kind of fluorinated monomer, rather than monomer (I) is mixed with a kind of nonfluorinated latex.
The median size of different latex can be different, yet preferably mixed phase or uses and has the fluoridize latex of mean sizes less than nonfluorinated latex like the latex of size.
Can be between 0 to 80 ℃ in temperature, mix latex under the atmospheric pressure conditions, use to be higher than under the non-pressurized pressure can not cause big improvement during the course.
To fluoridize latex introduces and to cause a kind of being equivalent to be introduced in resulting result when fluoridizing in the latex when nonfluorinated latex in the nonfluorinated latex.
In addition, when mixing two kinds of latex, a kind of latex is incorporated in the another kind of latex and does not cause that coalescent the and destabilization of dispersion is essential.For this reason, it must be compatible making the stable emulsifying agent of each latex particle: these emulsifying agents are oppositely charged not, preferably has the negatively charged ion and/or the nonionogenic tenside of similar hydrophilic for two kinds of latex.
In order to strengthen the colloidal stability of two kinds of dispersion mixtures, also can allow the emulsifying agent of other quantity or the protective colloid of other quantity are joined in this mixture as Walocel MT 20.000PV, although resulting mixture generally is stable especially.
The present invention also relates to attempt to constitute the composition of hydrophobic coating, as the japanning used in the building field, leather with varnish or finishing agent, fabric with finishing agent or timber with protection varnish, it is characterized in that they comprise at least a latex as defined above.
Following embodiment further specifies the present invention, but does not limit the present invention.In an embodiment, consumption represents that with weight part in each embodiment, the total consumption of monomer is 100 parts.-TRIFEMA: methacrylic acid 2,2,2-trifluoro ethyl ester-ALLYLMA: allyl methacrylate-MMA: methyl methacrylate-AA: vinylformic acid-MAA: methacrylic acid-E
2HA: 2-EHA-BUA: butyl acrylate-NMA: N hydroxymethyl acrylamide-EA: ethyl propenoate-DDM: lauryl mercaptan-NP25EO: the NONYL PHENOL ETHOXYLATED-NPS25EO that contains 25mol oxyethane: the NONYL PHENOL ETHOXYLATED sulfuric ester-DE (%) that contains 25mol oxyethane: dry extract, according to iso standard 1625 (1977) measurement-MFT (℃): minimum film-forming temperature, according to iso standard 2115 (1976) measurement- (mm): median size, with the Lo of company " MALVERN Instruments " classification
The automatic sieve of-C is measured this instrument application quasi-elastic light scattering principle.-water contact angle (°): the contact angle with moisture content of filming; By adopting Xisi, famous beauty in the late Spring and Autumn Period's machine with 250 μ m
The latex of specific thickness is deposited on the sheet glass, then in room temperature
Dry 8 hours and the method for spending the night under 40 ℃ of conditions are carried out under the condition
Film forming; Be the rule of placing in 50% the room more than 2 days in temperature then
Decide to measure contact angle with protractor on the plate; Carry out with two times of distilled water
Measure, required contact angle numerical value is more than or equal to 90 °.-naphthalene contact angle (°): filming as mentioned above has the contact angle of naphthalene; Using method is with mutually top
With, different is to adopt the purifying naphthalene to measure.-surface tension γ s
The statistics and convergence embodiment 1 (reference) of EXAMPLE Example 1 to 9 (reference): TRIFEMA
The mixture of 49 parts of softening waters, 0.05 part of NP25EO, 0.25 part of NPS 25EO and 0.35 part of sodium metabisulfite is added in the 5-1 reactor that is equipped with center mechanical stirrer, nitrogen air inlet and water condenser, and uses heating in water bath.
Be heated to after 67 ℃ with the survival gas in the nitrogen eliminating reactor and with reactor, add the preemulsion of 45 parts of water, 50 parts of MMA, 47 parts of BUA, 1 part of AA, 1 part of NMA, 1 part of TRIFEMA, 0.45 part of NP25EO and 2.25 parts of NPS25EO and be dissolved with the catalytic solution of 0.35 part of ammonium persulphate in 6 parts of softening waters, be 4 hours 30 minutes reaction time.
During adding preemulsion and catalytic solution, bathe mild stirring speed and remain on 67 ℃ and 200rpm respectively.When reinforced finishing, bathe temperature remain on 67 ± 1 ℃ 1 hour 30 minutes.
With the dispersion cooling, filtration and adding contain 20%NH then
3The aqueous solution transfer pH to 9.
Dispersions obtained characteristic records is in following table 1.
Embodiment 2 to 9 (reference) repeats the program of embodiment 1, is adjusted at used monomer composition in the polymerization at every turn.Also with used composition and dispersions obtained characteristic records in table 1, with the band water contact angle as the performance of filming that obtains by the latex coalescence effect.
The statistics and convergence reaction of table 1-TRIFEMA
| Embodiment | 2* | 1 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
| Monomer is formed (weight part) MMA | 51 | 50 | 49 | 48 | 46 | 42.2 | 35.5 | 19.4 | 0 |
| BUA | 47 | 47 | 47 | 47 | 47 | 45.8 | 42.5 | 0 | 0 |
| AA | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| NMA | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| E 2HA | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 38.6 | 37 |
| TRIFEMA | 0 | 1 | 2 | 3 | 5 | 10 | 20 | 40 | 61 |
| Dispersions obtained characteristic DE (%) | 49.9 | 52.0 | 50.0 | 50.0 | 50.0 | 50.0 | 50.0 | 50.3 | 50.4 |
| MFT(℃) | 16 | 19.5 | 18 | 19 | 17.5 | 17.5 | 17.5 | 10 | 9.5 |
| (nm) | 147 | 161 | 139 | 151 | 161 | 140 | 155 | 216 | 212 |
| The character that is obtained to film by the latex coalescence effect: water contact angle (°) | 78.5 | 78.9 | 76.7 | 78.9 | 79.1 | 80.5 | 82.3 | 88.5 | 92.0 |
* embodiment 2 is reference examples (not having TRIFEMA)
These results show, must increase TRIFEMA content widely, so that obtain useful hydrophobic property, i.e. and water contact angle degree 〉=90 °.In fact, by statistics and convergence TRIFEMA, must make content between 40 to 60% (weight), so that make its characteristic fit.Embodiment 10: polymerization TRIFEMA is to obtain structure particles
The mixture of 49 parts of softening waters, 0.05 part of NP25EO, 0.25 part of NPS 25EO and 0.35 part of sodium metabisulfite is added in the 5-1 reactor that is equipped with center mechanical stirrer, nitrogen air inlet and water cooling reflux exchanger, uses heating in water bath then.
Be heated to after 67 ℃ with the gas in the nitrogen eliminating reactor and with reactor, add first preemulsion of 37.8 parts of water, 38.6 parts of MMA, 49.7 parts of BUA, 0.9 part of AA, 1 part of NMA, 0.38 part of NP 25EO and 1.89 parts of NPS 25EO simultaneously and be dissolved with 0.31 part of ammonium persulphate catalytic solution in 5.3 parts of water, be more than 4 hours reaction time.
After finishing these materials of adding, add by 7.2 parts of softening waters, 0.1 part of AA, 10 parts of TRIFEMA, 5.7 parts of E
2Second preemulsion of HA, 0.07 part of NP 25EO and 0.36 part of NPS 25EO composition reaches and be dissolved with 0.04 part of ammonium persulphate catalytic solution in 0.7 part of water, and be more than 30 minutes reaction time.
During adding preemulsion and catalytic solution, bathe mild stirring speed and remain on 67 ℃ and 200rpm respectively.When reinforced finishing, bathe temperature remain on 67 ± 1 ℃ 1 hour 30 minutes.With the dispersion cooling, filtration and adding contain 20%NH then
3The aqueous solution is transferred to 9 with pH.
This dispersion of gained and made characteristic records of filming are in following table 2.
Embodiment 11:
Repeat the program of embodiment 10, first preemulsion the last the 1/3rd reinforced in 0.2 part of ALLYLMA of adding.
This dispersion of gained and made characteristic records of filming are in following table 2.
Embodiment 12 to 16:
Repeat the program of embodiment 10, adjust the composition (also listing in the table 2) of preemulsion, have the dispersion characteristic that obtains thus and water contact angle degree as the performance of filming by the coalescent gained of latex.
Table 2
A. first preemulsion last 1/3rd reinforced in the ALLYLMA of adding.B. first preemulsion last 1/4th reinforced in the ALLYLMA of adding.
*These percentage ratios are to obtain with respect to monomer sum (according to circumstances, for first or for second preemulsion)
| Embodiment | 10 | 11 | 12 | 13 | 14 | 15 | 16 | ||||||||
| Part | ％ * | Part | ％ * | Part | ％ * | Part | ％ * | Part | ％ * | Part | ％ * | Part | ％ | ||
| The composition of first preemulsion (nuclear) | Monomer total water MMA BUA AA NHA NP 25EO NPS 25EO ALLYLMAa, b | 90.2 37.8 38.6 49.7 0.9 1 0.38 1.89 0 | 42.8 55.1 1.0 1.1 | 90.4 37.8 38.6 49.7 0.9 1 0.38 1.89 0.2a | 42.7 55.0 1.0 1.1 0.2 | 96.2 43.2 44.2 50.0 0.95 1 0.43 2.16 0 | 46.0 52.0 1.0 1.0 | 92.6 41.7 47 43.7 0.93 1 0.42 2.08 0 | 50.6 47.1 1.0 1.1 | 58.0 39.7 40.3 45.6 0.94 1 0.40 1.98 0.2a | 45.6 51.8 1.0 1.1 0.2 | 84.3 37.9 38.7 43.7 0.84 1 0.38 1.09 0.1b | 45.9 51.8 1.0 1.2 0.1 | 84.3 37.9 38.7 43.7 0.84 1 0.38 1.09 0.1a | 45.9 51.8 1.0 1.2 0.1 |
| The composition of second preemulsion (shell) | Monomer total water NMA AA NMA TRIFRMA K2HA NP 25EO NPS 25EO | 15.8 7.2 0 0.1 0 10 5.7 0.07 0.36 | 0.6 63.3 36.1 | 15.8 7.2 0 0.1 0 10 5.7 0.07 0.36 | 0.6 63.3 36.1 | 4 1.8 0 0.05 0 2.5 1.45 0.02 0.09 | 1.2 62.5 36.3 | 7.37 3.3 0 0.07 0 5 2.3 0.03 0.17 | 1.0 67.4 31.2 | 11.86 5.3 0 0.06 0 7.5 4.3 0.05 0.27 | 0.5 63.2 36.2 | 15.86 7.1 0 0.16 0 10 5.7 0.07 0.36 | 1.0 63.1 35.9 | 15.86 7.1 0.16 0 10 5.7 0.07 0.36 | 1.0 63.1 35.9 |
| The characteristic of dispersion | DE(％) (nm) MFT(℃) | 50.8 199 10 | 50.4 177 11.5 | 51.3 134 10 | 50.0 154 11.5 | 50.0 174 10 | 49.5 174 11 | 51.6 161 10 | |||||||
| Because the performance of the coalescent gained film of latex | The water contact angle degree (°) | 92 | 93 | 94 | 90.4 | 93 | 97.2 | 94.2 | |||||||
The contact angle measuring result that is write down in the table 2 has been indicated as and has obtained having filming of hydrophobic performance and use the synthetic numerical value with the structure particles that is rich in TRIFEMA (60-65%) shell.
General content is that TRIFEMA (embodiment 10 to 16) the gained result between 2.5 to 10% (weight) is better than basically with 61% (weight) ration statistics polymerization TRIFEMA gained result (embodiment 9).Application Example 17 to 21: prepare japanning from a kind of TRIFEMA dispersion that contains
Preparation has the house japanning of following prescription:
Component weight part parts by volume softening water ... 78.0 106.7 contain the test dispersion of the dry extract of 50.2% (weight) ... 481.6 658.6 first groups
Non-associative thickener (32 weight %) 4.7 6.4 by COATEX company merchandising " VISCOATEX 46 " by name
Sterilant (100%) by " RIEDEL DE HAEN " company's merchandising " MERGAL K6N " by name ... 2.0 2.7
Mould inhibitor (100%) 2.0 2.7 by PHAGOGENE institute merchandising " PARMETOL DF19 " by name
Wetting agent by " BK-Ladenburg " company merchandising " CALGON N " by name, (100%) dispersion agent of the commodity " COATEX P190 " by name sold by " COATEX " company of 0.8 ingredients weight parts parts by volume O.6, (40 weight %) ... 3.0 4.1 second groups
Be called the defoamer (100%) of " DE HYDRAN1620 " by the commodity of " HENKEL-NOPCO " company sale ... 1.1 1.5 NH
3(22%) ... 1.2 1.6 commodity by the sale of " TIOXIDE " company are called the TiO of " TR 92 "
2140.7 48.1
Be called the lime carbonate (filling out 64.7 32.8 material) of " DURCAL 2 " by the commodity of " OMYA " company sale
Be called the lime carbonate (filler) of " DURCAL 10 " by the commodity of " OMYA " company sale ... 141.9 71.9
Be called the mica (filler) of " MICARVOR 20 " by the commodity of " KAOLIN " company sale ... 51.6 25.2
Propylene glycol
(solubility promoter) ... 15.2 20.8
Coalescing agent by " EASTMAN KODAK " company's merchandising " TE XANOL " by name ... 9.6 the 3rd group of 13.1 ingredients weight parts parts by volume
Defoamer (100%) by " HENKEL NOPCO " company's merchandising " DEHYDRAN 1620 " by name ... 1.1 1.5
Associative thickener (50 weight %) by " SERVO DELDEN " company's merchandising " SER AD FX1010 " by name ... 1.0 1.4
1000.0 1000.0
To disperse first group of component at a slow speed 5 minutes, under agitation progressively add second group of component then.This mixture of high speed dispersion 20 minutes, and cooling.Under agitation progressively add the 3rd group of component at last.
Therefore be used in embodiment 14,11,10,2 and 8 dispersions obtained preparation japannings.
In table No.3, the characteristic that gained is filmed is described.
Table No.3 is to the perviousness of water vapor
| Application example | The example dispersion | Water contact angle (℃) | The naphthalene contact angle (℃) | (g/m 2/24h) |
| 17 18 19 20 21 | 14 11 10 2 8 | 96.0 97.5 93.8 80.3 90.6 | 45.7 43.0 36.7 23.8 40.6 | 169 166 169 183 116 |
The structure particles dispersion japanning that containing of being prepared has TRIFEMA content according to embodiment 17,18 and 19 is made films and films and have bigger hydrophobicity and oleophobic property than comprising the contrast dispersion of embodiment 2 (no TRIFEMA) and comprise the embodiment 8 dispersion gained with statistics adding TRIFEMA of 40% according to embodiment 21 on the other hand according to embodiment 20 on the one hand.In addition, when use has the dispersion of core-shell particle, the perviousness of filming to water vapor is reduced to less degree.These results have confirmed that further the performance that gained is filmed surpasses the dispersion that does not cooperate.Embodiment 22 to 29: preparation is used for the dispersion of leather and fabric finish composition
Embodiment 22:
The mixture of 75 parts of softening waters, 0.3 part of NPS 25EO, 0.3 part of sodium metabisulfite is added to is equipped with center magnetic stirrer and nitrogen air inlet and is equipped with in the 5-1 reactor of reflux exchanger.
With the gas in the nitrogen eliminating reactor, reactor is heated to 55 ℃ subsequently then.When reaching this temperature, first preemulsion that contains 62.1 parts of softening waters, 49.9 parts of EA, 30.6 parts of MMA, 7.7 parts of AA, 1.8 parts of NMA and 2.43 parts of NPS 25EO of adding 10%, and add 10% by being dissolved with the catalytic solution that 0.3 part of ammonium persulphate is formed in 6 parts of water, reaction times is more than 15 minutes, maintains the temperature at 55 ℃ simultaneously.
Kept 15 minutes when bathing 55 ℃ of temperature, and then continue to add first preemulsion and add catalytic solution, the reaction times is 2 hours more than 15 minutes.
When the adding one of first preemulsion is finished, just add second preemulsion that comprises 6.9 parts of softening waters, 5.32 parts of EA, 3.63 parts of TRIFEMA, 0.85 part of AA, 0.2 part of NMA, 0.03 part of DDM and 0.27 part of NPS 25EO, continue simultaneously to add remaining catalytic solution and maintain the temperature at 55 ℃.
Finish when reinforced one, just, be cooled to room temperature then, and filter the strainer that passes through 30 μ m reaction mixture heating 1 hour to 80 ℃.
Branch is got the dispersion characteristic records in table 4.
Embodiment 23 to 29:
Repeat the program of embodiment 22, adjust the composition of preemulsion at every turn.In these compositions and dispersions obtained characteristic records table 4 below, have because the performance (contact angle) that the coalescent gained of latex is filmed.
Table 4
| 22 | 23 * | 24 | 25 | 26 | 27 | 28 | 29 ** | ||||||||||
| Part | ％ *** | Part | ％ *** | Part | ％ *** | Part | ％ *** | Part | ％ *** | Part | ％ *** | Part | ％ *** | Part | ％ *** | ||
| First preemulsion, the second prefabricated emulsus | Monomer total water MMA EA AA NMA HPS 25EO ALLYLMA TRIFEMA monomer total water MMA EA AA NMA TRIFEMA K2HA NPS 25EO DDM | 90 62.1 30.6 49.9 7.7 1.8 2.43 0 0 6.9 5.32 0.85 0.2 3.63 0.27 0.03 | 34.0 55.4 8.5 2.0 0 0 0 53.2 8.5 2.0 36.3 0 | 100 69 31 58.4 8.5 2 2.70 0 0 - - - - - - - - - | 31 54.4 8.5 2 0 0 - - - - - - | 80.2 55.2 27.4 44.4 6.8 1.6 2.16 0 0 13.8 0 10.64 1.7 0.4 7.26 0 0.54 0.06 | 34.2 55.4 8.5 2.0 0 0 0 53.2 8.5 2.0 36.3 0 | 80.2 55.2 27.4 44.4 6.8 1.6 2.16 0 0 13.8 0 10.64 0.4 0.4 8.56 0 0.54 0.06 | 34.2 55.4 8.5 2.0 0 0 53.2 2.0 2.0 42.8 0 | 95.0 65.5 32.3 52.7 8.1 1.9 2.27 0 0 3.45 0 0.11 0.43 0.1 3 1.36 0.13 0.02 | 34.0 55.5 8.5 2.0 0 0 0 2.2 8.6 2.0 60.0 27.2 | 90.2 62.1 30.6 49.9 7.7 1.8 2.43 0.2 0 6.9 0 1.75 0.2 6 1.85 0.27 0.035 | 33.9 55.3 8.5 2.0 0.2 0 0 17.5 2.0 2.0 60.0 18.5 | 90.1 62.1 36.4 49.9 1.8 1.4 2.43 0.2 0 6.9 0 1.75 0.2 0.2 6 1.85 0.27 0.035 | 40.3 55.3 2.0 2.0 0.2 0 0 17.5 2.0 2.0 60.0 18.5 | 100 69 0 50.5 8.3 2 2.70 0 39 - - - - - - - - - | 0 50.5 8.5 2.0 0 39 - - - - - - |
| %TRIFEMA in shell | 36.3 | - | 36.3 | 42.8 | 60 | 60 | 60 | - | |||||||||
| The weight % of shell | 10 | - | 20 | 20 | 5 | 10` | 10 | - | |||||||||
| DE(％) MFT(℃) (nm) | 42 9 162 | 43.5 5 162 | 40.7 2 174 | 40.2 3 166 | 41.2 3 151 | 40.4 18 158 | 39.4 18 159 | 40.5 9.5 208 | |||||||||
| Water contact angle degree in the time of 20 ℃ (°) water contact angle degree in the time of 160 ℃ (°) | 74 | 63.6 73.6 | 77.3 86.3 | 86.6 87 | 66.4 93.5 | 69.2 88.6 | 70.0 88.7 | 78.8 80.6 | |||||||||
* embodiment 23 is reference examples of statistics and convergence reaction, does not have TRIFEMA,
* embodiment 29 is statistics and convergence reaction reference examples of TRIFEMA.
* * is with respect to monomeric sum, and it is (according to circumstances, pre-for first to obtain these percentage ratios
The system milk sap or for second preemulsion).
The thickness of embodiment 22 to 29 expressions fluoridizing shell and composition are to the influence of the hydrophobic performance of filming.With respect to reference examples (embodiment 23) and with respect to the statistics latex of the embodiment 29 that comprises 39 parts of TRIFEMA, TRIFIMA is joined in the shell of core-shell particle and make the hydrophobic property of filming represent a significant improvement.Application Example 30 to 34: preparation fabric and leather finishing agent
(embodiment 30 to 34, respectively): the black pigment of-commercial goods " LEP TON " by name with following method preparation embodiment 23 (reference examples), 22,24,25 and 29 latex ... 20%-latex ... 30%-water ... 50%
Be sprayed on these compositions on the leather and drying under 60 ℃ of conditions.According to a kind of dynamic water tolerance method (ASTM standard 2099-77 1973) and according to a kind of method (NFG 52 301) of measuring the quick friction of translation of leather dyestuff or coating, the characteristic of the expression leather of handling.
Under the comparing result in 5 of tabulating.
Table 5
| Embodiment | 30 | 31 | 32 | 33 | 34 |
| The dispersion of embodiment | 23* | 22 | 24 | 25 | 29 |
| The total amount % of TRIFEMA | 0 | 3.6 | 7.26 | 8.56 | 39 |
| Structure particles | Statistics | Nuclear-shell | Nuclear-shell | Nuclear-shell | Statistics |
| Number of times ASTM 2099-70 is moved in deflection | 352±138 | 375±228 | 1078±155 | 947±457 | 1804±441 |
| Moistening quick friction * * | 1 | 3 | 2 | 3.5 | 1 |
* contrast
This result's of * mark: 1=is not so good;
5=is better
Testing shows that deflection moves number of times and increase along with the increase of the add-on of TRIFEMA, and has increased the wet abrasion intensity of filming.These results confirm aspect the hydrophobic performance that strengthens protective cover, by the TRIFEMA role.Will be noted that by the method for polymerization TRIFEMA in a material shell, improved moistening quick frictional property greatly.Embodiment 35 (reference): preparation does not have the latex of TRIFEMA
The mixture of 49 parts of softening waters, 0.05 part of NP 25EO, 0.25 part of NPS 25EO and 0.35 part of sodium metabisulfite is joined in the 5-1 reactor that center mechanical stirrer, nitrogen air inlet and water condenser be housed, adopt heating in water bath then.Getting rid of the gas of reactor with nitrogen and reactor is being heated to after 67 ℃, add a kind of preemulsion of being made up of 45 parts of water, 51 parts of MMA, 47 parts of BUA, 1 part of AA, 1 part of NMA, 0.45 part of NP 25EO and 2.25 parts of NPS 25EO simultaneously and a kind ofly be dissolved with 0.35 part of ammonium persulphate catalytic solution in 6 parts of softening waters, the reaction times is 4 hours 30 minutes.
During adding preemulsion and adding catalytic solution, bathe temperature and agitator speed and remain on 67 ℃ and 200rpm respectively.When adding is finished, bath temperature keep 67 ± 1 ℃ 1 hour 30 minutes.Then dispersion is cooled off, filtered and add and contain 20%NH
3The aqueous solution is transferred pH to 9.
Dispersion gained characteristic is reached because the performance that the coalescent gained of latex is filmed is listed in the table 6.
Embodiment 36 and 37 (reference)
Repeat the program of embodiment 35, adjust each time and be applied to monomeric composition in the polyreaction.
With dispersion gained characteristic and since the performance that the coalescent gained of latex is filmed also list in the table 6.
Table 6
Embodiment 38 to 42: embodiment 37 fluoridizes latex/embodiment 35 nonfluorinated latex mixtures
| Embodiment | 35 | 36 | 37 | |
| Used monomeric composition | MMA | 51 | 19.4 | 0 |
| BUA | 47 | 0 | 0 | |
| AA | 1 | 1 | 1 | |
| NMA | 1 | 1 | 1 | |
| E 2HA | 0 | 38.6 | 37 | |
| TRIFEMA | 0 | 40 | 61 | |
| Dispersions obtained and characteristic | DE％ | 52.0 | 50.3 | 50.4 |
| MFT(％) | 19.5 | 10 | 9.5 | |
| nm | 161 | 216 | 212 | |
| Because the performance that the coalescent gained of latex is filmed | Water contact angle (°) | 72.9 | 88.5 | 92.2 |
| Surface tension (mN/m) γ s | 31.8 | 27.5 |
The nonfluorinated latex of fluoridizing latex and enforcement 35 of embodiment 37 is mixed, prepare five kinds of different mixtures (embodiment 38 to 42) of forming respectively.
In table 7, write down the coalescent film performance that obtains owing to these latex mixtures, also write down those character of fluoridizing latex and nonfluorinated latex of embodiment 37 and 35 simultaneously respectively.
Table 7
| Embodiment | The dispersion of embodiment 37 | The dispersion of embodiment 35 | ％ TRIFEMA | Water contact angle (°) | γ s (mN/m) |
| 37 | 100 | 0 | 61 | 92.2±0.4 | 27.5 |
| 38 | 20 | 80 | 12.2 | 89.6±1.5 | 29.0 |
| 39 | 10 | 90 | 6.1 | 92.7±2.0 | 29.6 |
| 40 | 8 | 92 | 4.9 | 91.6±1.8 | 29.8 |
| 41 | 6 | 94 | 3.7 | 89.2±2.4 | 27.4 |
| 42 | 4 | 96 | 2.4 | 90.7±2.2 | 23.9 |
| 35 | 0 | 100 | 0 | 78.5±1.0 | 31.8 |
Filming of obtaining shown the hydrophobic performance of filming and being equal to mutually that can obtain with only using fluorinated film separately by latex mixture is coalescent, thereby shown the meaning that this technology will reduce for the weight content of the required TRIFEMA of the protective cover that obtains to have hydrophobic performance.Embodiment 43 to 45: the nonfluorinated latex of fluoridizing latex/embodiment 35 of embodiment 11 mixes
Thing
Adopt with embodiment 38 to 42 in identical method, the latex of fluoridizing among the embodiment 11 is mixed with nonfluorinated latex among the embodiment 35, prepare the mixtures of difference composition.
Results of comparison in table 8.
Table 8
| Embodiment | The dispersion % of embodiment 11 | The dispersion % of embodiment 35 | ％ TRIFEMA | Water contact angle (°) | γ s (mN/m) |
| 11 | 100 | 0 | 10 | 92.6±1.5 | 30.6 |
| 43 | 50 | 50 | 5 | 92.2±0.4 | 24.4 |
| 44 | 30 | 70 | 3 | 91.8±1.0 | 27.5 |
| 45 | 20 | 80 | 2 | 92.7±1.0 | 27.1 |
| 35 | 0 | 100 | 0 | 78.5±1.0 | 31.8 |
Equally in this case, notice the maintenance of hydrophobic property when adding nonfluorinated latex, make the content of TRIFEMA be low to moderate 2% composition and can access useful characteristic.Mixing of the non-chloride latex of fluoridizing latex and embodiment 35 of embodiment 46 and 47: embodiment 10
Compound
Embodiment 10 synthetic are in varing proportions fluoridized latex and embodiment 35 synthetic nonfluorinated latex preparation latex mixtures.Results of comparison in table 9.
Table 9
| Embodiment | The dispersion % of embodiment 10 | The dispersion % of embodiment 35 | ％ TRIFEMA | Water contact angle (°) | γ s (mN/m) |
| 10 | 100 | 0 | 10 | 92.7±1.9 | 29.5 |
| 46 | 50 | 50 | 5 | 92±0.5 | 25.5 |
| 47 | 20 | 80 | 2 | 93±1.0 | 27.3 |
| 35 | 0 | 100 | 0 | 78.5±1.0 | 31.8 |
Also notice in embodiment 46 and 47, fluoridize the significant improvement that the hydrophobic property of latex obtains.
Embodiment 48 and 49 (application examples)
Fluoridize latex preparation mixture (embodiment 48 and 49) with nonfluorinated latex among the embodiment 23 and the statistics among the embodiment 29.
Form these mixtures then in the following manner: the black pigment of-commercial goods name " LEPTON " ... 20%-latex mixture (or with reference to latex) ... 30%-water ... 50%
These compositions are sprayed on the leather, and dry under 60 ℃ of conditions.According to embodiment 30 to 34 described methods, the feature of the expression leather of handling.
Its outcome record is in table 10.
Table 10
| Embodiment | The dispersion % of embodiment 23 | The dispersion % of embodiment 29 | ％ TRIFEMA | Number of times ASTM 2099-70 is moved in deflection | Temperature is friction fast |
| 23 | 100 | 0 | 0 | 352±158 | 1 |
| 48 | 87.5 | 12.5 | 4.88 | 1595±235 | 3 |
| 49 | 75 | 25 | 3.75 | 2325±533 | 2.5 |
| 29 | 0 | 100 | 39 | 1804±441 | 1 |
With respect to reference examples (embodiment 23) and with respect to the latex (embodiment 29) of the TRIFEMA that contains a large amount of statistical distribution, fluoridize latex and all be improved with making its abrasion intensity and wet flexural strength mixing of nonfluorinated latex.
Embodiment 50 and 51
Fluoridize the latex preparation mixture with the nonfluorinated latex of embodiment 23 and the nucleocapsid structure of embodiment 25.
Will be owing to the coalescent gained coating characteristic of latex is recorded in the table 12.
Table 12
| Embodiment | The dispersion % of embodiment 25 | The dispersion % of embodiment 23 | ％ TRIFEMA | Water contact angle (°) | γ s (mN/m) |
| 25 | 100 | 0 | 8.56 | 86.6 | 25.5 |
| 50 | 50 | 50 | 4.28 | 88.8 | 25.4 |
| 51 | 30 | 70 | 2.57 | 86.0 | 27.1 |
| 23 | 0 | 100 | 0 | 63.6 | 35.8 |
Notice that also in the middle of the mixing of these latex, the hydrophobic property of this coating is improved.
Claims (19)
1. fluoridize (methyl) acrylic latex by a kind of particle dispersion or by what a kind of mixture of particle dispersion was formed, these dispersions are with single order section at least, letex polymerization obtains in water medium, wherein the perfluorinated monomers of one or more formulas (I) expression:
In the formula:
-R
1Represent CH
3Perhaps H,
-R
2Represent perfluor C
1-C
10Alkyl, and
-0＜n≤4，
As forming the unique fluorinated monomer of particulate, and be statistical distribution in the statistics particle, wherein this particle formed in a stage, perhaps statistical distribution in the shell of the structure particles of nuclear-shell or nuclear-middle layer-shell type, wherein said core-shell particle generates in the two-stage polyreaction, and examine-middle layer-shell structure granules is to generate in the polyreaction more than the two-stage, described latex is describedly fluoridized that the structure particles dispersion constitutes or is made of at least a nonfluorinated statistics particulate dispersion and at least a described dispersion and/or at least a described mixture of fluoridizing statistics particulate dispersion of fluoridizing structure particles by a kind of
What one or more formulas (I) monomer representative was less than 80% (weight) fluoridizes the structure particles shell,
With the total monomer consumption that is used to form all described latex particles is benchmark, and the monomeric ratio of formula (I) is between 1.8 and 20% (weight).
2. latex according to claim 1 is characterized in that, monomer (I) is (methyl) vinylformic acid 2,2, the 2-trifluoro ethyl ester.
3. according to any one described latex in claim 1 and 2, it is characterized in that, is benchmark with the total monomer consumption that is used to form all described latex particles, and the monomeric ratio of formula (I) is between 2 and 10% (weight).
4. according to any one described latex in claim 1 and 2, it is characterized in that the polymer glass transition temperature that constitutes described statistics particle or described structure particles stage is lower than or equals 40 ℃.
5. latex according to claim 4 is characterized in that, the polymer glass transition temperature that constitutes described statistics particle or described structure particles stage is between-5 to 25 ℃.
6. according to any one described latex in claim 1 and 2, it is characterized in that, fluoridize the monomer (by weight, total amount is 100 weight %) composed as follows of adding up particle or fluoridizing the structure particles shell:
At least a monomer of-20-80% (I),
-20-80% is at least a can to produce (methyl) vinylformic acid or the vinyl monomer with low glass transformation temperature homopolymer,
-0-30% is at least a can to produce (methyl) vinylformic acid with high glass transformation temperature homopolymer, vinylbenzene or vinyl monomer,
At least a carboxylic acid of-0-10% (methyl) Acrylic Acid Monomer,
-0-3% at least a crosslinked (methyl) Acrylic Acid Monomer, and
-0-5% at least a hydrophilic (methyl) Acrylic Acid Monomer.
7. latex according to claim 6 is characterized in that, fluoridizes the monomer (by weight, total amount is 100 weight %) composed as follows of adding up particle or fluoridizing the structure particles shell:
At least a monomer of-35-70% (I),
-20-55% is at least a can to produce (methyl) vinylformic acid or the vinyl monomer with low glass transformation temperature homopolymer,
-0-15% is at least a can to produce (methyl) vinylformic acid with high glass transformation temperature homopolymer, vinylbenzene or vinyl monomer,
At least a carboxylic acid of-0-2% (methyl) Acrylic Acid Monomer,
-0-2% at least a crosslinked (methyl) Acrylic Acid Monomer, and
-0-2% at least a hydrophilic (methyl) Acrylic Acid Monomer.
8. according to any one described latex in claim 1 and 2, it is characterized in that nonfluorinated statistics particle and the monomer (by weight, total amount is 100 weight %) composed as follows of fluoridizing structure particles nuclear:
-20-80% is at least a can to produce (methyl) vinylformic acid or the vinyl monomer with low glass transformation temperature homopolymer,
-20-80% is at least a can to produce (methyl) vinylformic acid with high glass transformation temperature homopolymer, vinylbenzene or vinyl monomer,
At least a carboxylic acid of-0.5-10% (methyl) Acrylic Acid Monomer,
-0.3-5% at least a crosslinked (methyl) Acrylic Acid Monomer, and under structure particles nuclear situation,
But-0-0.3% is compatible monomer of at least a difunctionality or an at least a difunctionality grafted monomer under the N hydroxymethyl acrylamide situation at cross-linking monomer.
9. latex according to claim 8 is characterized in that, nonfluorinated statistics particle and the monomer (by weight, total amount is 100 weight %) composed as follows of fluoridizing structure particles nuclear:
-40-70% is at least a can to produce (methyl) vinylformic acid or the vinyl monomer with low glass transformation temperature homopolymer,
-30-60% is at least a can to produce (methyl) vinylformic acid with high glass transformation temperature homopolymer, vinylbenzene or vinyl monomer,
At least a carboxylic acid of-0.5-2.5% (methyl) Acrylic Acid Monomer,
-0.5-3% at least a crosslinked (methyl) Acrylic Acid Monomer, and under structure particles nuclear situation,
But-0-0.2% is compatible monomer of at least a difunctionality or an at least a difunctionality grafted monomer under the N hydroxymethyl acrylamide situation at cross-linking monomer.
10. latex according to claim 6 is characterized in that:
-can produce (methyl) Acrylic Acid Monomer to be selected from ethyl propenoate with low glass transformation temperature homopolymer, butyl acrylate, vinylformic acid 2-ethylhexyl ester and vinylformic acid ester in the ninth of the ten Heavenly Stems, and
-hydrophilic (methyl) Acrylic Acid Monomer is ethyl imidazol(e) ketone (methyl) acrylate or acrylamide.
11. latex according to claim 8 is characterized in that:
-can produce (methyl) Acrylic Acid Monomer to be selected from ethyl propenoate with lower glass transition temperatures homopolymer, butyl acrylate, 2-EHA and vinylformic acid ester in the ninth of the ten Heavenly Stems,
-can to produce the vinyl monomer with low glass transformation temperature homopolymer be 2-ethyl acid vinyl acetate,
-can to produce (methyl) Acrylic Acid Monomer with high glass transformation temperature homopolymer be methyl methacrylate,
-can to produce the vinyl monomer with high glass transformation temperature homopolymer be vinyl acetate,
-carboxylic acid (methyl) Acrylic Acid Monomer is vinylformic acid or methacrylic acid,
-cross-linking monomer is N-methylol (methyl) acrylamide, (isobutoxy methyl) acrylamide, and two (methyl) vinylformic acid glycol ester, two (methyl) vinylformic acid butanediol ester, two (methyl) vinylformic acid hexylene glycol ester or methacrylic anhydride,
But-compatible or grafted monomer is a diallyl maleate, (methyl) allyl acrylate and tetramethylene dimethacrylate.
12., it is characterized in that the part by weight that structure is fluoridized particle shell is represented the described particle of 3 to 30% (weight) according to any one described latex in claim 1 and 2, this particle size is between 100 to 300nm.
13. latex according to claim 12 is characterized in that, the part by weight that structure is fluoridized particle shell is represented the described particle of 5 to 20% (weight), and this particle size is between 100 to 300nm.
14., it is characterized in that this granule density is 10 to 65% (weight) of total dispersion weight according to any one described latex in claim 1 and 2.
15. latex according to claim 14 is characterized in that, this granule density is 40 to 55% (weight) of total dispersion weight.
16. as the preparation method of latex as described in any one in the claim 1 to 15, it is characterized in that, what prepare at least a nuclear-shell or nuclear-middle layer-shell structure fluoridizes (methyl) acrylic particles water dispersion, and one or more monomers (I) participate in the composition of described particle shell; Its feature is that also if target is nonfluorinated statistics particle and the mixture of fluoridizing structure particles, the water dispersion of then one or more dispersions of gained and at least a nonfluorinated being added up (methyl) acrylic particles mixes; Perhaps its feature also is alternatively, adopt one or more formulas (I) compound to prepare at least a water dispersion of fluoridizing statistics (methyl) acrylic particles as comonomer, and its feature is that also the water dispersion of one or more dispersions of gained and at least a nonfluorinated being added up (methyl) acrylic particles mixes; Perhaps its feature also is alternatively, the dispersion of at least a nonfluorinated statistics (methyl) acrylic particles is added up the particulate water dispersion and at least a described water dispersion of fluoridizing structure particles mixes with at least a described fluoridizing, all above-mentioned water dispersions be in water medium under statistics particle situation by a stage emulsion polymerisation process or under the structure particles situation by making more than the emulsion polymerisation process in a stage
What one or more formulas (I) monomer representative was less than 80% (weight) fluoridizes the structure particles shell,
With the total monomer consumption that is used to form all described latex particles is benchmark, and the monomeric ratio of formula (I) is between 1.8 and 20% (weight).
17. method according to claim 16 is characterized in that, during the polyreaction of shell, is benchmark with the monomer that adds, adding is up to 0.5% (weight) and is selected from alkyl sulfhydryl, the chain-transfer agent of Thiovanic acid and composition thereof.
18. method according to claim 17 is characterized in that, during the polyreaction of shell, is benchmark with the monomer that adds, and adds and is up to 0.3% described chain-transfer agent.
19. japanning or varnish, leather or fabric are coated with decorative composition, it is characterized in that comprising at least a as any one described latex in the claim 1 to 15.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9412431A FR2725721B1 (en) | 1994-10-18 | 1994-10-18 | LATEX AND MIXTURES OF FLUORINATED ACRYLIC AND METHACYL LATEX, THEIR MANUFACTURING PROCESSES AND THEIR APPLICATIONS IN THE FIELD OF HYDROPHOBIC COATINGS |
| FR9412431 | 1994-10-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1130640A CN1130640A (en) | 1996-09-11 |
| CN1087310C true CN1087310C (en) | 2002-07-10 |
Family
ID=9467966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95118631A Expired - Fee Related CN1087310C (en) | 1994-10-18 | 1995-10-17 | Fluorinated acrylic and methacrylic latices and mixtures thereof, processes for manufacturing them and their application in field of hydrophobic coatings |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US5798406A (en) |
| EP (1) | EP0708120B1 (en) |
| JP (1) | JP3125977B2 (en) |
| KR (1) | KR0174644B1 (en) |
| CN (1) | CN1087310C (en) |
| AT (1) | ATE166894T1 (en) |
| CA (1) | CA2160734C (en) |
| CZ (1) | CZ271195A3 (en) |
| DE (1) | DE69502791T2 (en) |
| FR (1) | FR2725721B1 (en) |
| GR (1) | GR3027771T3 (en) |
| TW (1) | TW320638B (en) |
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- 1995-10-17 AT AT95402315T patent/ATE166894T1/en not_active IP Right Cessation
- 1995-10-17 CA CA002160734A patent/CA2160734C/en not_active Expired - Fee Related
- 1995-10-17 CN CN95118631A patent/CN1087310C/en not_active Expired - Fee Related
- 1995-10-18 US US08/544,693 patent/US5798406A/en not_active Expired - Lifetime
- 1995-10-18 JP JP07294730A patent/JP3125977B2/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| KR0174644B1 (en) | 1999-04-01 |
| JPH08208936A (en) | 1996-08-13 |
| GR3027771T3 (en) | 1998-11-30 |
| EP0708120A1 (en) | 1996-04-24 |
| JP3125977B2 (en) | 2001-01-22 |
| DE69502791D1 (en) | 1998-07-09 |
| ATE166894T1 (en) | 1998-06-15 |
| CA2160734A1 (en) | 1996-04-19 |
| DE69502791T2 (en) | 1999-01-21 |
| CA2160734C (en) | 2002-01-01 |
| TW320638B (en) | 1997-11-21 |
| FR2725721B1 (en) | 1998-12-04 |
| KR960014231A (en) | 1996-05-22 |
| EP0708120B1 (en) | 1998-06-03 |
| CN1130640A (en) | 1996-09-11 |
| CZ271195A3 (en) | 1996-05-15 |
| FR2725721A1 (en) | 1996-04-19 |
| US5798406A (en) | 1998-08-25 |
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